organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

3-Meth­­oxy-4-(prop-2-yn-1-yl­­oxy)benzaldehyde

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aDepartment of Inorganic Chemistry, Guindy Campus, University of Madras, Chennai 600 025, India
*Correspondence e-mail: bala2010@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 9 November 2016; accepted 2 December 2016; online 9 December 2016)

In the title compound, C11H10O3, the prop-2-yn-1-yl group is inclined to the benzene ring by 69 (7)°. In the crystal, mol­ecules are linked by a pair of C—H⋯O hydrogen bonds, forming inversion dimers with an R22(12) ring motif. The dimers are linked by a second C—H⋯O hydrogen bond, forming sheets parallel to the (102) plane. The sheets stack along the c-axis direction with a separation of ca 3.4 Å.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

Vanillin and vanillin derivatives are used in food and non-food applications, in fragrances and as flavouring agents for pharmaceutical products (Hocking, 1997[Hocking, M. B. (1997). J. Chem. Educ. 74, 1055-1059.]; Walton et al., 2003[Walton, N. J., Mayer, M. J. & Narbad, A. (2003). Phytochemistry, 63, 505-515.]). Synthetic vanillin is used as an inter­mediate in chemical and pharmaceutical industries for the production of herbicides, anti­foaming agents and drugs, such as papaverine, L-dopa and L-methyl­dopa, as well as anti­microbial agents such as trimethoprim (Fitzgerald et al., 2005[Fitzgerald, D. J., Stratford, M., Gasson, M. J. & Narbod, A. (2005). J. Agric. Food Chem. 53, 1769-1775.]). In the past few years, 1,2,3-triazole mol­ecules have been synthesized which can be employed as chemotherapeutic agents for various diseases (Wang et al., 2008[Wang, S., Wang, Q., Wang, Y., Liu, L., Weng, X., Zhang, G. L. X. & Zhou, X. (2008). Bioorg. Med. Chem. Lett. 18, 6505-6510.]). In particular, vanillin when treated with propargyl bromide forms propargyloxybenzaldehyde which is linked via a 1,2,3-triazole ring with an alkane side arm (Ahmed Kamal et al., 2011[Kamal, A., Prabhakar, S., Janaki Ramaiah, M., Venkat Reddy, P., Ratna Reddy, Ch., Mallareddy, A., Shankaraiah, N., Lakshmi Narayan Reddy, T., Pushpavalli, S. N. & Pal-Bhadra, M. (2011). Eur. J. Med. Chem. 46, 3820-3831.]). We report herein on the synthesis and crystal structure of a new vanillin derivative.

The mol­ecular structure of the title compound is illustrated in Fig. 1[link]. The prop-2-yn-1-yl group (C1≡C2—C3) is inclined to the benzene ring by 69 (7)°.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound, showing the atom labelling and 50% probability displacement ellipsoids.

In the crystal, mol­ecules are linked by a pair of C—H⋯O hydrogen bonds, forming inversion dimers with an [R_{2}^{2}](12) ring motif (Table 1[link] and Fig. 2[link]). The dimers are linked by a second C—H⋯O hydrogen bond, involving the propynyl group (H1), forming sheets parallel to plane (102); see Table 1[link] and Fig. 2[link]. The sheets stack along the c-axis direction, with a separation of ca 3.4 Å, but with no significant inter­molecular inter­actions being present.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3A⋯O2i 0.97 2.42 3.374 (2) 166
C1—H1⋯O3ii 0.93 2.39 3.274 (2) 158
Symmetry codes: (i) -x, -y+1, -z; (ii) [-x+1, y-{\script{1\over 2}}, -z-{\script{1\over 2}}].
[Figure 2]
Figure 2
The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines (see Table 1[link]) and, for clarity, only H atoms H1 and H3A (grey balls) have been included.

Synthesis and crystallization

4-Hy­droxy-3-meth­oxy­benzaldehyde (0.378 g, 2.48 mmol) and anhydrous K2CO3 (0.414 g, 3.0 mmol) were dissolved in 15 ml of dry DMF and propargyl bromide (1 g, 2.48 mmol) was added. The reaction mixture was stirred at room temperature for 24 h, and then poured into 100 ml of water and extracted with CHCl3. The organic phases were combined and washed with water, brine solution, dried over anhydrous sodium sulfate and the solvent evaporated under vacuum. The crude product was purified by column chromatography using silica gel (hexa­ne/ethyl acetate = 4:1 v/v) and the title compound was obtained as a yellow solid (yield 0.915 g, 78%; m.p. 458 K). The compound was dissolved in acetone and slowly evaporated to give brown block-like crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C11H10O3
Mr 190.19
Crystal system, space group Monoclinic, P21/c
Temperature (K) 296
a, b, c (Å) 11.8560 (6), 11.8836 (6), 6.8348 (4)
β (°) 92.044 (1)
V3) 962.36 (9)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.10
Crystal size (mm) 0.35 × 0.30 × 0.25
 
Data collection
Diffractometer Bruker Kappa APEXII CCD
Absorption correction Multi-scan (SADABS; Bruker, 2004[Bruker. (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.961, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections 10764, 1896, 1528
Rint 0.020
(sin θ/λ)max−1) 0.617
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.093, 1.07
No. of reflections 1896
No. of parameters 129
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.15, −0.13
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004[Bruker. (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SIR92 (Altomare et al., 1993[Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343-350.]), SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Structural data


Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

3-Methoxy-4-(prop-2-yn-1-yloxy)benzaldehyde top
Crystal data top
C11H10O3F(000) = 400
Mr = 190.19Dx = 1.313 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4115 reflections
a = 11.8560 (6) Åθ = 2.4–28.4°
b = 11.8836 (6) ŵ = 0.10 mm1
c = 6.8348 (4) ÅT = 296 K
β = 92.044 (1)°Block, brown
V = 962.36 (9) Å30.35 × 0.30 × 0.25 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD
diffractometer
1896 independent reflections
Radiation source: fine-focus sealed tube1528 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ω and φ scanθmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2004)
h = 1414
Tmin = 0.961, Tmax = 0.980k = 1414
10764 measured reflectionsl = 88
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.093 w = 1/[σ2(Fo2) + (0.0353P)2 + 0.2349P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
1896 reflectionsΔρmax = 0.15 e Å3
129 parametersΔρmin = 0.13 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0104 (19)
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.25864 (14)0.36251 (15)0.2945 (3)0.0699 (5)
H10.29470.34190.40770.084*
C20.21334 (12)0.38838 (13)0.1523 (3)0.0539 (4)
C30.15648 (13)0.41756 (12)0.0269 (2)0.0547 (4)
H3A0.08650.37550.03170.066*
H3B0.20390.39550.13900.066*
C40.22014 (11)0.60814 (11)0.06716 (18)0.0383 (3)
C50.33237 (11)0.57799 (12)0.09667 (19)0.0433 (3)
H50.35270.50240.09970.052*
C60.41399 (11)0.65991 (12)0.12150 (19)0.0445 (3)
H60.48930.63940.14080.053*
C70.38435 (11)0.77230 (11)0.11782 (18)0.0416 (3)
C80.27149 (11)0.80274 (11)0.09066 (18)0.0403 (3)
H80.25160.87840.09020.048*
C90.18929 (11)0.72245 (11)0.06453 (18)0.0379 (3)
C100.04141 (14)0.85726 (13)0.0341 (3)0.0610 (4)
H10A0.06200.89140.15760.091*
H10B0.03900.86070.01310.091*
H10C0.07730.89690.06910.091*
C110.46886 (14)0.86149 (14)0.1404 (2)0.0579 (4)
H110.44240.93520.14180.069*
O10.13206 (8)0.53520 (8)0.03999 (15)0.0511 (3)
O20.07696 (8)0.74270 (8)0.03513 (15)0.0518 (3)
O30.56883 (10)0.84848 (12)0.1572 (2)0.0815 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0562 (10)0.0683 (12)0.0853 (13)0.0013 (8)0.0054 (9)0.0240 (10)
C20.0445 (8)0.0405 (8)0.0762 (11)0.0023 (6)0.0035 (7)0.0097 (7)
C30.0559 (9)0.0348 (8)0.0739 (10)0.0050 (6)0.0070 (8)0.0006 (7)
C40.0421 (7)0.0379 (7)0.0349 (6)0.0026 (6)0.0015 (5)0.0017 (5)
C50.0475 (8)0.0389 (7)0.0431 (7)0.0049 (6)0.0024 (6)0.0015 (6)
C60.0402 (7)0.0542 (9)0.0390 (7)0.0019 (6)0.0016 (5)0.0036 (6)
C70.0464 (8)0.0466 (8)0.0321 (6)0.0061 (6)0.0052 (5)0.0040 (6)
C80.0513 (8)0.0358 (7)0.0341 (6)0.0002 (6)0.0054 (5)0.0016 (5)
C90.0410 (7)0.0407 (7)0.0320 (6)0.0030 (6)0.0020 (5)0.0019 (5)
C100.0585 (9)0.0513 (9)0.0729 (11)0.0178 (8)0.0019 (8)0.0047 (8)
C110.0568 (10)0.0608 (10)0.0568 (10)0.0121 (8)0.0107 (7)0.0090 (7)
O10.0439 (6)0.0375 (5)0.0720 (7)0.0023 (4)0.0033 (5)0.0072 (5)
O20.0434 (6)0.0431 (6)0.0684 (7)0.0068 (4)0.0034 (5)0.0062 (5)
O30.0540 (8)0.0867 (10)0.1042 (10)0.0200 (7)0.0096 (7)0.0199 (8)
Geometric parameters (Å, º) top
C1—C21.168 (2)C6—H60.9300
C1—H10.9300C7—C81.3921 (19)
C2—C31.460 (2)C7—C111.463 (2)
C3—O11.4311 (17)C8—C91.3711 (18)
C3—H3A0.9700C8—H80.9300
C3—H3B0.9700C9—O21.3612 (16)
C4—O11.3647 (16)C10—O21.4251 (17)
C4—C51.3858 (18)C10—H10A0.9600
C4—C91.4068 (18)C10—H10B0.9600
C5—C61.3789 (19)C10—H10C0.9600
C5—H50.9300C11—O31.1968 (19)
C6—C71.3812 (19)C11—H110.9300
C2—C1—H1180.0C8—C7—C11118.51 (13)
C1—C2—C3178.47 (18)C9—C8—C7120.80 (12)
O1—C3—C2112.64 (13)C9—C8—H8119.6
O1—C3—H3A109.1C7—C8—H8119.6
C2—C3—H3A109.1O2—C9—C8125.69 (12)
O1—C3—H3B109.1O2—C9—C4115.16 (11)
C2—C3—H3B109.1C8—C9—C4119.15 (12)
H3A—C3—H3B107.8O2—C10—H10A109.5
O1—C4—C5125.57 (12)O2—C10—H10B109.5
O1—C4—C9114.47 (11)H10A—C10—H10B109.5
C5—C4—C9119.96 (12)O2—C10—H10C109.5
C6—C5—C4120.10 (13)H10A—C10—H10C109.5
C6—C5—H5120.0H10B—C10—H10C109.5
C4—C5—H5120.0O3—C11—C7126.07 (16)
C5—C6—C7120.23 (13)O3—C11—H11117.0
C5—C6—H6119.9C7—C11—H11117.0
C7—C6—H6119.9C4—O1—C3118.26 (11)
C6—C7—C8119.76 (12)C9—O2—C10117.21 (11)
C6—C7—C11121.73 (13)
C1—C2—C3—O1174 (100)C5—C4—C9—O2179.79 (11)
O1—C4—C5—C6179.69 (12)O1—C4—C9—C8179.94 (11)
C9—C4—C5—C60.66 (19)C5—C4—C9—C80.26 (18)
C4—C5—C6—C70.2 (2)C6—C7—C11—O32.6 (2)
C5—C6—C7—C80.6 (2)C8—C7—C11—O3176.98 (15)
C5—C6—C7—C11178.98 (12)C5—C4—O1—C34.62 (19)
C6—C7—C8—C90.97 (19)C9—C4—O1—C3175.72 (12)
C11—C7—C8—C9178.59 (12)C2—C3—O1—C469.00 (17)
C7—C8—C9—O2179.39 (11)C8—C9—O2—C100.92 (19)
C7—C8—C9—C40.55 (18)C4—C9—O2—C10179.13 (12)
O1—C4—C9—O20.11 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O2i0.972.423.374 (2)166
C1—H1···O3ii0.932.393.274 (2)158
Symmetry codes: (i) x, y+1, z; (ii) x+1, y1/2, z1/2.
 

Acknowledgements

TE is grateful to the University of Madras, Chennai, for financial support (URF). The authors thank the SAIF, IIM, Chennai, India, for recording the single-crystal X-ray data, and V. Maheshwaran, Department of Crystallography and Biophysics, University of Madras, for solving the crystal structure.

References

First citationAltomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350.  CrossRef Web of Science IUCr Journals Google Scholar
First citationBruker. (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFitzgerald, D. J., Stratford, M., Gasson, M. J. & Narbod, A. (2005). J. Agric. Food Chem. 53, 1769–1775.  CrossRef CAS Google Scholar
First citationHocking, M. B. (1997). J. Chem. Educ. 74, 1055–1059.  CrossRef CAS Google Scholar
First citationKamal, A., Prabhakar, S., Janaki Ramaiah, M., Venkat Reddy, P., Ratna Reddy, Ch., Mallareddy, A., Shankaraiah, N., Lakshmi Narayan Reddy, T., Pushpavalli, S. N. & Pal-Bhadra, M. (2011). Eur. J. Med. Chem. 46, 3820–3831.  CrossRef CAS Google Scholar
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWalton, N. J., Mayer, M. J. & Narbad, A. (2003). Phytochemistry, 63, 505–515.  Web of Science CrossRef PubMed CAS Google Scholar
First citationWang, S., Wang, Q., Wang, Y., Liu, L., Weng, X., Zhang, G. L. X. & Zhou, X. (2008). Bioorg. Med. Chem. Lett. 18, 6505–6510.  CrossRef CAS Google Scholar

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